Reaction product of haloalkylthiophenes and hydroxyaryl compounds



Patented Nov. 7, 1950 REACTION PRODUCT OF HALOALKYLTHIO= PHENES ANDHYDROXYARYL COMPOUNDS John H. McCrackeu, Corpus Christi, Tex., assiguortheir formation.

to Socony-Vacuum Oil Company, Incorporated, a corporation of New York NoDrawing. Application May 28, 1947, Serial No. 751,123

12 Claims. 1

This invention relates to a new group of compositions of matter formedby the interaction of haloalkylthiophenes and hydroxyaryl compounds andto mineral oil compositions containing these new materials.

Haloalkylthiophenes such, for examglf, u chioromethylthiophene are knownand ay be prepared according to the procedure outlined by Blicke andBurckhalter in the Journal of the American Chemical Society, volume 64,pa e 477 sired.

compounds,

against discoloration and oxidation.

amples of the numerous new compositions of matter that may be preparedand utilized in accordance with the general principles of thisinvention.

Example I In a 3-necked flask fitted with a mechanical stirrer anddropping funnel, were placed 200 cc. of benzene and 38 g. (0.405 mol) oiphenol. The solution was cooled in an ice bath and a solution of 18 g.(0.135 mol) of chioromethylthiophene (prepared by the procedure outlinedby Blicke and Burckhalter in Journal of American Chemical Society, vol.64, page 477 (1942) except that the procedure was simplified by usingliquid hydrochloric acid (instead of gaseous hydrochloric acid)dissolved in 25 cc. of benzene) was added dropwise over 1% hours time.Hydrogen chloride was evolved in copious amounts.

After standing at room temperature ior several hours, the benzenesolution was washed first with water, then with sodium bicarbonatesolution and then twice again with water to remove the hydrochloricacid. The benzene and excess phenol were removed by distillation atreduced pressure and the yield of unpurified material proved to be about85% based on the amount of chloromethylthiophene used.

Purification was effected by dissolving the product in benzene,decolorizing with an ad- (1942). The corresponding ethyl, propyl andsorptive clay and crystallizing from a benzenebutyl compounds may alsobe prepared, and the petroleum ether mixture. The purified materialthiophene may be additionally substituted, was a white, crystallinesolid, melting at 59-60 either before or after converting it into the C.On treatment with chloracetic acid in alkahaloalkyl derivative, by otherradicals, if so de line solution, t material yielded a c p nd which wasapparently p-(Z-thenyl) phenoxy= In accordance with the presentinvention, it acetic acid, melting at 108.5-109.5 C. The has beendiscovered that haloalkylthiophenes, theoretical neutralization number(milligrams of either with or without additional substituents in KOHrequired to neutralize the acids in one the thiophene ring, may bereacted with hyram of pr du t) r this a d s 248. horr droxyarylcompounds, such as phenols and mentally, it was determined to be 249.7.It was naphthols, either substituted or unsubstituted, to thereforeassumed that the new composition of form new compositions of matter,which are matter formed by this example was a y a apparentlythienylalkyl aryl hydroxy compounds. n ca o p und; P- 2- theny1)phenoi;These may either be substituted by reason of 2d 5 substituents in theoriginal thiophene or aryl nuclei, or may have substituents insertedafter It has further been discovered that the new Example H whenincorporated in minor Isobutylene was bubbled into a solution of amountsin oil compositions, stabilize the oil p-(2-thenyDphenol (prepared inaccordance with Example I) and 5% by weight of concen- The followingexamples illustrate the general trated sulphuric acid, inchloroform.This was principles of this invention, but it is to be undercontinueduntil the reaction temperature stood that they represent but a fewpossible exdropped slightly. After washing and distilling oil thesolvent, the product was distilled and a fraction boiling at -180 C. at4 mm. of mercury pressure was collected. This product was washed withcaustic to remove any unreacted starting material and the result was amobile, yellow oil. This product is believed to have the followingstructural formula:

C(CHa):

QHOOH Starting with p(2-thenyl) phenol, 5 by weight 68 or concentratedsulphuric acid was added, and an other by weight of a 5% solution ofboric acid was also added. This mixture was diluted with about 25% byweight of benzene and isobutylene was passed slowly into the mixture ata temperature of about 70 C. After /2 hour, another 25% of benzene wasadded and the passing of isobutylene into the mixture continued forabout 2 additional hours. The acid was then removed by washingtheproduct with a sodium bicarbonate solution and the solvent wasremoved by distillation. The residue was vacuum distilled and thefraction boiling at 180 to 210 C. at 3 mm. of mercury pressure wascollected as the product. It was a mobile yellow oil which darkened onexposure to air. The formula should be:

s H Tom-Q01; (CEO:

The calculated sulphur content should be 10.6% v

and upon analysis it was found to be 11.52%.

Example IV portion of aqueous formaldehyde to a starting mixture oft-butylthiophene in concentrated hydrochloric acid. The resultantcompound 5-tbutyl-2-chlormethylthiophene is a colorless liquid boilingat 86-98 C. at 3 mm. of mercury pressure.

Solutions of 3.5 g. (0.019 mol) of the above product and 6 g. (0.064mol) of phenol in chloroform were mixed and heated to reflux temperaturefor 0.5 hour. The product was washed and the solvent removed as before.The residue was distilled under reduced pressure and the fractionboiling at 163-170 C. at 2 mm. of mercury pressure was collected as aproduct. This product is believed to be:

s crime-W Tom-Own Example V To a solution of 26 g. (0.18 mol) ofalphanaphthol in 150 cc. of chloroform contained in an Erlenmeyer flaskwas added a solution of 12 g. (0.09 mol) of chlormethylthiophene in 25cc. of chloroform. The solution was refluxed for 1 hour. After washingand removing the solvent by Q mmo By calculation it should have a.sulphur content of 13.3%. It was actually found by analysis to have asulphur content of 13.2%

Example VI A reaction between chlormethyllhiophene and beta-naphthol wascarried out in the same manner as the reaction with alpha-naphthol inEx- The calculated sulphur content again is 13.3%. By analysis it wasfound to-be 10.42%.

Example VII In an effort to produce additional new compounds and inaddition to definitely flx the formula of the compound produced byExample III, p-(5-t-butyl-2-thenyl)phenol was alkylated by the procedureoutlined in Example II, which should be a product of the followingstructure:

CHmGT JAJHPO- This product had a boiling point of 185-193" C. at 3 mm.of mercury pressure and a refractive index (11 of 1.5494 as compared toa refractive index 01.1.5474 for the product of Example 111.

Example VIII By reacting 5 t butyl 2 chlormethylthiophene with 2-butylphenol in the manner described'in Example IV, a product was producedwhich was substantially identical with the product of Example VII,having a boiling point of 180-195 C. at 3 mm. of mercury pressure and anindex of refraction of 1.5494.

The eflicacy of the above materials in improving the characteristics ofmineral oil may be seen from the following examples. In some of theseexamples, a compound was used which is believed to be 2,4 bis (Z-thenyl)phenol. This compound was recovered from the residue of the reactions ofchlormethylthiophene with phenol in Example I. It is a yellow liquid,which darkens on standing, boils at 195-210 C. at 2 mm. of mercurypressure. On analysis, it shows 21.47% sulphur, whereas theoretically itshould contain 22.38% sulphur. The oils used in the following exampleswere:

S. U. V. at Flash Point, Specific 011 F. F. Gravity Example IX A numberof tests have been made on blends of the products of the above exampleswith a highly refined oil suitable for use in transformers. In thefollowing table this oil is designated as Oil A. This oil was preparedby treating a Coastal distillate with 40 pounds of 98% sulphuric acidand pounds of 103% oleum per barrel. This was followed by washing andpercolating through clay. This type of oil tends to form acidic productson oxidation. It was tested by heating samples to 120 C. and bubblingoxygen through them for 70 hours. The oxidation was then'determined bytitrating with an I alcoholic solution of data obtained for the oilalone and for the oil 5. potassium hydroxide. The

Composition:

Oil A+0.2% 2-t-butyl-4-(5-t-butyl-2- thenyl) phenol prepared inaccordance with Example VIII 0.02

Oil A+0.2% 2-t-butyl-4-(5-t-butyl-2- thenyl) phenol prepared inaccordance with Example IX 0.02 Oil A+0.2% 2,4-bis (Z-thenyl) phenol006' Example X A number of tests have also been made on blends of theproducts of the above examples with a distillate from a Rodessa crudewhich was refined with furfural, dewaxed and filtered. This oil isdesignated Oil B. It is an oil suitable for use in steam turbines. Thisoil was tested by the Brown-Boveri turbine test method which involvesheating a test sample of the oil in the presence of a piece of copperfoil, at a temperature of 110 C. in air, and for '72 hours. At the endof the test, the color and Neutralization Number of the sample aredetermined and these are indicative of the extent to which the oil isaffected by oxidation. The following results were obtained:

Color Neutraliza- Lovibond tion Number thenyDpheiiol rielpared inaccordance thenyhphenol prepared in accordance with Exam le .0299 p 9.885 3 an ass Example XI A number of tests have also been made on blendsof the product of the above examples with a mixed Mid-Continent andCoastal distillate which has been refined by treatment with '70 poundsof 98% sulphuric acid per barrel. This oil is designated Oil C. Thetreated oil is then neutralized, washed and filtered through clay. Oil Cand Oil 13 were tested in accordance with the following test: The testconsists in placing ml. of oil to be tested in each of four 150 x 25 mm.test tubes, each covered with a glass lid and provided with a 5 mm.delivery tube extending 6 to the bottom. Nine iron nails (1.0101 g.) anda copper coil (24 in. of No. 8 wire) are also placed in each tube.During the test the tem-" perature is maintained at 91 C. and clean, dryair is bubbled through the oil at 5 liters per hour. Also 2 ml. ofdistilled water are added once every 24 hours. Samples are removed fromthe test 1 bath after varying periods of time and examined for acidity(neutralization number) and color.

The following results were obtained:

Color Neutraliza- I Levibond tion Number Oil B 166 50 a3 a 162 1.5 0.02011 B+0.2% p-(Z-thenyl) phenoL 308 5 0.02 886 32 3.7 011 B+0.2%2-t-butyl-4-(2 5 0.04 thenyl) phenol 262 6 2. l 011 B+0.272,6-di-t-butyl-4-(2- 144 7 thenyl) phenol 1 a 011 B+0.2% p-(5-t-butyl-2-162 9 0.04 thenyl) phenol 720 15 1. 4 011 B+0.2% (Z-thenyD-alpha napthol167 22 0.12 011 B+0 2% (2-thenyl)-beta- 188 15 0.02 naphthol 15 0. 04011 B+0.2'7 2 t-butyl4-(5-t- 9 buz l-z-meil l phenol g is 8; Oil Bl-0.2% 2,4bis (2-thenyl} 3 & 3-? Pheml 73s 14 111 a 162 19 1.0 312 623.9

162 4 0.02 Oil C+0.2% D-(Z-thenyl) phenol. 306 20 .03 5,000 less than1.0 011 C+0.2% 2,4-bis (Z-thenyl) 331 1.5 0.01

phenol 978 V 20 0.9

Although the new compounds may be added in a wide range of percentagesto mineral oils, it has been found, as illustrated by the foregoingexamples, that quantities ranging from 0.05% to 0.2% will usuallystabilize mineral oils satisfactorily against oxidation anddeterioration. In some instances, however, it may be found desirable toadd amounts up to 1% for this purpose.

There is nothing to prevent the preparation of compounds of the newseries having alkyl side chains of any length. Solubility of thesecompounds in mineral oils improves, generally, with length of alkyl sidechains. Alkyl groups of any length are satisfactory, although it isprobable that when the alkyl side chains are excessively long, lessefiect per weight of material may be encountered since the alkyl sidechains themselves are probably inert. For this reason, in oilcompositions, it is preferred to use compounds of the new series inwhich no alkyl side chain is of any greater length than those which maybe derived from petroleum wax, and, preferably, to use compounds inwhich no alkyl side chain is of no more than about six carbon atoms inlength.

It is contemplated by this invention that the new reaction products ofhaloalkyl thiophenes and hydroxyaryl compounds will be incorporated inlubricating oil compositions in amounts sufficient to improve thecharacteristics thereof. The basic materials to which these improvingagents are to be added may be generally described as mineral lubricatingoils of the type normally used in internal combustion engines. Such oilsare generally produced from petroleum, but may be produced syntheticallyor derived from other sources. It is contemplated that the principles ofthis invention may be applied to lighter petroleum products such asgasoline and kerosene, or to heavier petroleum products of the nature ofpetroleum gear lubricants, petrolatum jellies and petroleum waxes. Otheraddition agents may be present in the composition for the pur-' pose ofimproving the composition in other or in the same respects as thecompositions are improved by the addition of the products of thisinvention.

This invention also contemplates the preparation and marketing of thereaction products of this invention alone, oiin the form of oilconcentrates, that is, mixtures of the reaction products of thisinvention with oil, in which the reaction products are present inquantities in excess of that required to improve the characteristics ofthe oil, so that the concentrates may be mixed with a larger quantity ofoil to improve its characteristics. In-such concentrates, the reactionproducts may be present in concentrations ranging as high as 50%, andany other desired addition agents may also be present.

What is claimed is:

1. A composition of matter having the formula:

wherein A is a radical selected from the group consisting of 2-thenyland an alkyl-substituted 2-thenyl in which the alkyl substituent is lessthan about 6 carbon atoms in length, and B is a radical selected fromthe group consisting of hydroxy-phenyl, hydroxy-naphthyl, analkylsubstituted hydroxy-phenyl and an alkyl-substitutedhydroxy-naphthyl, in which the alkyl substituents are less than about 6carbon atoms in length.

2. A composition of matter having the formula:

3. A composition of matter having the formula:

I H 0 (CH1): Uri 1):

4. A composition of matter having the formula:

WCQEOOH 5, A composition of matter having the formula:

(CHQIClSLEG '7. A mineral oil containing a minor proportion, suflicientto stabilize the oil against discoloration and oxidation, of I acomposition of matter having the formula:

wherein A is a radical selected from the group consisting of 2-thenyland an alkyl-substituted 2-thenyl in which the alkyl substituent is lessthan about 6 carbon atoms in length, and B, is a radical selected fromthe group consisting of hydrcxy-phenyl, hydroxy-naphthyl, analkylsubstituted hydroxy-phenyl and an alkyl-substitutedhydroxy-naphthyl, in which the alkyl substituents are less than about 6carbon atoms in length.

8. A mineral oil containing from about 0.05% and up to about 1% of acomposition of matter having the formula:

s & I

9. A mineral oilcontaining from about 0.05%

and up to about 1% of a composition of matter having the formula:

(CHI):

10. A mineral oil containing from about 0.05% and up to about 1% of acomposition of matter having the formula:

,CMQE M. I

11. A mineral oil containing from about 0.05% and up to about 1% of acomposition of matter having the formula:

12. A mineral oil containing from about 0.05% and up to about 1% of acomposition of matter having the formula:

C(CHI)I WMUEO JOHN H. MccRAcKnN.

REFERENCES CITED The following references-are of record in the file ofthis patent:

UNITED STATES PATENTS Richter: Organic Chemistry," Wiley, 1938, pages649-650.

Caesar and Sachanen: Ind. Eng. Chem.," 40, 922 (1948).

7. A MINERAL OIL CONTAINING A MINOR PROPORTION, SUFFICIENT TO STABILIZETHE OIL AGAINST DISCOLORATION AND OXIDATION, OF A COMPOSITION OF MATTERHAVING THE FORMULA: